Cationic thiazole dyes and process for manufacturing the same



s 132 132 CATIONIC Tr-nAzoLE Dims AND PROCESS Fon MANUFACTURING THE SAME I Mitsuo Suzuki, Nakano-ku, Tokyo, Masao Iiz uka,

"Kanagawa-k'u, Yokohama, and Masao Yamamoto, Hodogaya-ku, Yokohama, Japan, assig'nors to Hodogaya Kagaku Kogyo Kabushih Keisha No Drawing, Filed*May.29,;1961, Ser. No. 113,110 Claims priority, application Japan'Jnne 2, 1960 4Claims. (Cl. 260-158) 7 a The present invention relates to a new series of useful basic monoazo-dyes of the general formula I v CHZQHQCONHQ and a process for manufacturingthe same. i In the above formula R stands for hydrogen atom or an unionizable radical as substituent, preferably an alkyl or alkoxy radical such asmethyl, ethyl,methoxy, ethoxy and ,phenoxy radical, R representshydrogeri atom or an aliphatic radical, R as well as R, means hydrogen atom, an aliphatic or-an araliphatic radical and X indicates an anion. The dyes according to the present invention exert very excellent dyeing properties on fibers made from polyacrylonitrile and copolymers thereof. The dyes obtained according to the present invention are characterized. by its .pos-

sessing a ,B-carbamoylethyl radical as a substituent at the tertiary amino nitrogen in thiazole ring of the above general formula.

. a Ithas already been known that a ben zothiazole azo compound having a quaternary nitrogen atom can be prepared by the reaction of an 'alklatingreagent selected from a variety. of compounds on the thiazole nitrogen ,qf'anazo-dye having a thiazole ring,;these compounds being exemplified by alkylchlorides, alkylbromide's,,'al-

kyliodides, aralkylhalides, dialkylsulfates, alkylbenzene- ,tsulfates, alky-p-rnethylbenzenesulfates (cf, for instance,

"Glau'ert, J. Chem. s e. 1953 3742 It is also known that cationic dyes prepared by the just mentioned'process United States Patent Patented May 5, 1964 fective in their rapidly retiring in solubility in water caused by some increased of molecular weight," the dyes of the present invention are suitable owing to their said large solubility to be used in printings of various objects. To speak of a further merit of the dyes according to the present invention, they are able to be applied at a moderate rate of dyeing without being weakened in their atr ty f p vao v on r e a d c p y e the e a manufactured into vario us articles. The rate o f dyeing with which said kinds of known cationic dyes are dyed on polyacrylonitrile fibers is so great that, as expected from reported pre eminent large activation energy of dyeing as comparedwrth other dispersion dyes and acidic ones, an even dyeing can hardly be attained for certain unless maintenance of a uniform temperature distribution throughout the dyeing bath and slow temperature -elevation of the bath-are carefully practiced. The excellence in the above connection of the dyes. of the present invention not only excludes the problem of mere ring dyeing but contributes to improving rubbing fastness. They are not less. better 7 than the known dyes also inthe aspect of light fastness as Well as washing fastness.

Now, through investigations on the method of preparing the present new useful cationic dyes, a new process for manufacturing'them was discoveredwhich proved very satisfactory not only. in its technical aspect but also, in

' the economical point of view. This invented process comprises lettingacrylamide react directly on a tertiary amine "of benzothiazole type, either subjected to no further processing or dissolved in a proper solvent, in the presence of an organic or inorganicacid capable of working as a proton-donor so as to'produce a quaternary basic monoazo-dye belonging in chemical structure to theaforeare applicable to dyeing of fibers manufacturedfrom polyacrylonitrile and copolymers thereof (of, for instance,

American Cyanamid Co.-U.S. 2,893,816)

However, being distinguished in chemical structure from'these known dyes as illustratedby the above general formul'en'the basic monoazo-dys according to the present invention are entirely novel in respect of that they have not appeared ever in literature. In addition, as compared with salts of the known. dyes, salts of the new dyes obtained according to the present invention proved to be of paramount use because of their exerting unexampled splendid dying properties on fibers made of polyacrylonivtrile and copolymers thereof. Thus, in the case ofmutual I identity of R R R and R in the general formula, for

instance, 'the strong auxochromic effect of carbainoyl- I ethyl group makes the dyes of the present invention as ap- 5 plied on polyacrylonitrile' fibers deepen the color tone of. the dye fibers to a remarkable extent, allowing a greenish blue dye totbe realized with ease This is quite a new matternever experienced with any dyes ever reported j in literature. In contrast with the' -known allieddyes de- I.

mentioned general formula. Because no reaction has ever been proposed which allows quaternary ammonium compounds to be produced by direct action of acrylamide on tertiary amino compoundsespeciallyof weak basicity,

the manufacturing process according to the. present invention is looked upon as a new'sort of chemical reaction, the process being illustrated .by. the following chemical schema: Y p

where R R R and R are in agreement in their meaning with the corresponding notations in the general formula given in the beginning of this specification. v

Although the present reactioncan proceed even in the absence of solvent, use of a solvent is preferable, especially such as effectively dissolves the tertiary amino 'compound employed as raw material. The preferable solvent 'is exemplified by alcohols such as ethanol, butanol; ethyleneglycol, ethers such as tetrahydrofuran, dioxan, dimethylformamide and methylamylketone, while suitable derivatives of hydrocarbones of benzene series such as nitroben zene, chlorobenzene'andetc; are also. available.

at a thus elevated teming quaternary amino compounds, a method is known according to which an alkylhalide, a sulfuric acid ester or a sulfonic acid ester is made to react on a ter tiary amino compound. Also the dyes according to the present invention can be obtained by making a halogenated propionic acid amide react on a tertiary amine compound of benzothiazole type. However, from the Weakness of the known process of necessitating special preparation of in an amount of 177 parts and acrylic acid amide of 355 .parts are dissolved in 1770 parts of glacial acetic acid. The mixture is then added with 47 parts of 35% hydrochloric acid, heated under thorough stirring to 90 C. and kept at this temperature for 3 hours in reaction. After completion of the reaction, a great portion of the glacial acetic acid is recovered, the content of the reaction vessel being then dissolved in 5000 parts of Water. The solution, after being freed from insoluble matters by filtration, if necessary, is added with 70 parts of zinc chloride and further with sodium chloride of an amount corresponding to of total weight of the mixture so as to cause the salt of dyeas reaction product to precipitate. Separating by filtration anddrying the precipitate, a blue dye is obtained which dissolves readily in'Water and dyes polyacrylonitrile fibers brilliantly. clear blue shade with an excellent fastness and level dyeing property.

Example 2 By working analogously to Example l-but using 189 parts of instead of 177 parts df Cz tOl Working, analogously to Example 1 but using 141 parts of i instead of a dye is obtained'which is excellent in fastness, having level dyeing property and dyes polyacrylonitrile fibers reddish blue shade.

' Example 4 By a reaction similar to that in Example 1 except the use of 163 parts of an'excellent fastness and level dyeing property, which dyespolyacrylonitrile fibers brilliant bluish violet shade.

Example 5 A compound amounting to 105 parts is "dissolved together with 71 parts of acrylic acid amide in 1000 parts of ethyleneglycol. The solution is then added with 500 parts of sodium chloride, heated under thoroughstirring till it acquires'a temperature of 100 C. and added with 250 parts of concentrated sulfuric acid drop by drop in a period of 2 hours. After the reaction was completed by keeping the temperature for further 2 hours at this temperature, a great portion of the ethyleneglycol is recovered and the residual portion is dissolved by adding 5000 parts of water, insoluble matters being filtered off, if necessary. The solution thus obtained is added with 70 parts of zinc chloride and further with'sodium chloride in an amount corresponding to 10% of total weight of j the solution so that the salt of dye produced may be precipitatedj The dyeobtained by drying the precipitate dissolves readily in water giving a blue-colored solution and dyes polyacrylonitrile fibers greenish blue shade; the color is brilliantly clear and excellent in fastness to light, rubbing and washing.

Example 6 I In 1000'parts of %.formic acid, 161 parts of a com- .pound and 284 parts of acrylic acid amide is thoroughly dissolved. A reaction is made to proceed by stirring the :solution for 2 hours at C. After the completion 70 ofreaction, the mixture is pouredin 210,000 parts of Water, completely dissolved and added first with 70 parts of zincchloride and then with sodium chloride amounti ing to 10% of total weight of the solution so that the r salt of dye as reaction product maybe precipitated. The dye obtained by separating by filtration and drying is as in leveling.

readily soluble in water and dyes polyacrylonitrile fibers reddish blue shade, having leveling, property 'andbeing very excellent in fastness.

Example 7 By Working similarlyto Example 6 but using 127 parts v of instead of 161 parts of a dye is 'obtained which dyes polyacrylonitrile fibers brilliant violet, the color being e xcellent, in fastness as well v Example t H 7 By a reactionwsimilar to that in Example 6 but with i 193 parts of 7 CgHs the color being excellent in fastness as well as in property oflevel dyeing. Example 9 Working similarly to Example 8 but using 187 parts of instead of p after a reactionextended for 45 hours, a dye is' obtained 'whichdyes polyacrylonitrile fibers greenish blue and has excellentfastness and property of level dyeing.

Example 10 In 1800 parts of glacial acetic acid, acompound s 1 CH3 7 C a i 1 v \C N=N 'N V amounting to 141 parts is dissolved together with 284 parts of acrylic acid amide. The solution is added with 183 parts of p-toluenesulfonic acid tetrahydrate), heated under thorough stirring to 90 C. and kept at this temperature for 2 hours till the reaction is completed. Then,

i a great portion of the glacial acetic acid is recovered under reduced pressure. The residual portion is then dissolved in 5000 parts of water, insoluble matters being removed,

6 7 if necessary,by filtrationg The solution is added first. with 7O parts of, zinc, chloride and then with. sodium chloride in an amount equal to 10% of total weight oi the solution so as to cause salt of dye to precipitate, The'dye 5 thus obtained dissolves quite'readilylin water, giving'rise to a reddish blue solution. It dyes polyacrylonitrile fibers 7 level dyeing and isexcellentin fastness.

a somewhat reddish blue shade which has property of Example l l subjecting 162 parts of CH /s\- i (ljHa 0:11, A. r a c-N=N N instead of p 'A o'-N=NON i for 5-6 hours to a reaction analogous to that in Example 10, adye is obtained which dyes polyacrylonitrile fibers reddish blue and is excellent in fastness as well as in level dyeing property. 1 a

I Example 12 Working similarly to' Example 10 but with 189 parts of CHzCHaCN instead of v 1 CH3; i i 0H3 a dye is obtained which dyes polyacrlylonitrile iibers greenish blue and is excellent in fastness and property of level dyeing.

"Example 13 Working analogously to Ex ample 11 but using 177 parts of instead of 51 s CH; 3

a dye is obtained which dyes polyacrylonitrile fibers rather pure blue as compared withthe dye obtainedin Example 11 and is excellent in fastness and in level dyeingproperty.

Example 14 In '1000 par t'slof ethylalcohol, 236 parts of a comp ound i y 0 \N/ i O i our,

and 107' parts of acrylic acid amide are dissolved. The I solution is added withi'lSO parts of 48% hydrobromic acid, heated under thorough stirring and subjected'to reaction for about 4 hours at a temperature corresponding to jthe boiling point of ethylalcohol. Then, a great portion iof the ethylalcohol is recovered under reduced pressure, the residual portionbeing dissolved in7500 parts of water.

The aqueous solution is added with 105 parts of zinc 'chloride and then with sodium chloride amounting to 8% o' f"total weight of the solution so that the salt of dye "produced maybe caused to precipitate. The dye thus obtained readily dissolves in water, yielding a blue solution, and dyes polyacrylonitrile fibers greenish blue, the 1 color being excellentin fastness aswell as in level dyeing property.

' *Example 15' Employing parts of v i and working analogously to Example 14, a dye is obtained which dyes polyacrylonitrile fibers a brilliant blue shade and is excellent in fastness and also in property of level dyeing. l

g Example 16 U or Working similarly to Example 14 but with 258 parts of Cz a instead of a dye is obtained which dyes polyacrylonitrile fibers a brilliant greenish blue shade .and is excellent in fastness and property of leveldyeing.

Example 17 Working analogously to Example 1 4 but using 212 parts of ou cmoi a dye is obtained after a reaction of 1 hour, which dyes polyacrylonitrile fibers a brilliant greenish blue shade and is excellent in fastness as well as in level dyeing property.

7 Example 18 Working similarly to Example 10 but that 170 parts of S t cmo- 1 02H5 i i e Ca s- CHzOIEhCl instead of l r v 8 r r and '119 parts of benzenesulfonic acid'are used instead N g t and p-toluenesulfonicacid, respectively, a dye is obtained by conducting the reaction for 4-5 hours, which dyes polyacrylonitrile fibers brilliant blue and is excellent in fastness and in level dyeing property.

Example 19' v In 1000 parts of dioxan, 204 parts ofa compound S v k: C1130 /CH2CH201 CN=N N\ N/ CH OH Cl and 284 parts of acrylic acid amide are dissolved. ,The solution is added with 700 parts of 8.0% formic acid and under stirring brought to 100 C. The mixture is added furtherWithSOO parts'of formic acid ,drop by drop in a duration of 2 hours. After completion of the addition of formic acid drops, the whole system is further agitated 0 property.

for about an hour to bring the reaction completed. Then,

the whole reaction mixture is poured into 10,000 parts of water, removed of insoluble matters by filtration, if necessary, added with parts of zinc chloride and further with sodium. chloride amounting to 10% of total weight of the solution so that the salt of dye as reaction product may be precipitated out of the solution. The dye obtained by filtrating and drying readily dissolves in Water, producing a blue solution. It has leveling property and dyes polyacrylonitrile fibers a brilliant greenish blue shade which is fast to light, washing and rubbing.

- Example 20 Working similarly to Example 19 but using 178 parts of s 7 I C2H6O /CH3 OHzCHzOH instead of c zC zCl CHzC zCl CHaO- H \N/ I a dye is obtained which dyes polyacrylonitrile fibers blue and is excellent in fastness as well as in level dyeing Example 21 Working analogously to Example 19 but using 148 parts of I x r a dye is obtained which dyes polyacrylonitrile fibers a somewhat reddish blue shade and has excellent fastness and property of level dyeing.

Q; t I Example 22 I In 2000 parts of nitrobenzene, 151 parts of a compound precipitated out of the solution. The dye thus obtained has a very large solubility in water and shows bluish violet color. It dyes polyacrylonitrile fibers a bluish violet shade which is excellent in fastness and also in level dyeing. V

We claim: I 1. Basic monoazo-dyes represented by a general frmula R C-N=N N\ X gg R} iHgCHgCONHz wherein R is a member selected from the'group consisting of hydrogen, lower alkyl and lower alkoxy, R ista member selected from the group consisting of hydrogen and lower alkyl, R and R each mean a member selected from the group consisting of hydrogen, lower alkyl, ethylchloride, ethylcyanide, benzyl, and ethylvbenzyl, and X indicates an anion.

2. A basic monoazo-dye represented by a structural formula a suitable solvent and in the 3. process for manufacturing basic monoazo-dyes consisting of that a compound represented by a general formula wherein R is a member selected from the group consisting of hydrogen, lower alkyl and lower alkoXy, R is a member selected from the group consisting of hydrogen and lower alkyl, R and R each mean a member selected from the group consisting of hydrogen, lower alkyl, ethylchloride, ethylcyanide, benzyl, and ethylbenzyl, is subjected to reaction directly with acrylic acid amide, the reaction being carried out at an elevated temperature in a suitable solvent and in the presence of an acid as a proton donor.

'4. A process for manufacturing a basic monoazo dye consisting of reacting a compound having the following formula:

CzHs N With acrylic acid amide at an elevated temperature in donor.

References Cited in the file of this patent UNITED STATES PATENTS Bossard et a1. Dec. 16, 1958 Tsang et al July 7, 1959 OTHER REFERENCES Hickenbottom, Reactions of Organic Compsl, 1948, 2nd ed., pages 24 and 25, Longmans, Green and C0.

presence of an acid proton 

1. BASIC MONAZO-DYES REPRESENTED BY A GENERAL FORMULA 